Silylphenoxyalcohols



Patented Feb. 5, 1952 sILrLPHsNoxxALooHoLs JohnL. Speier, Jr.,Pittsburgh, Pa., assigrior to Dow Corning Corporation, Midland, Micln, a

corporation of Michigan No Drawing. Application January 8, 1951, SerialNo. 205,031

4 Claims.

1 This invention relates to silylphenoxyalcohols. It is an object ofthis invention to prepare novel compositions of matter which are usefulas intermediates in the preparation of organosilicon polymers. Anotherobject is to prepare compounds which are useful as emulsifiers anddetergents.

This invention relates to compounds of the formula(CH3)3SiCsH4OCH2CHR'OH where R is a methyl radical or hydrogen.

Alcohols of the above type are prepared by hydrolyzing compounds of theformula (CH3) 3SiC'sH4OCH2CHR'OSiR3 in which R is a monovalenthydrocarbon radical.

' The hydrolysis is carried out under the normal conditions forhydrolyzing silane esters, such as by treating the ester with aqueousacid. If desired, a mutual solvent may be employed. The products of thereaction are the above alcohols and hexaorganodisiloxanes.

The silane esters are in turn prepared by reacting compounds of theformula RaSlOCHzCHROCeI-I4Cl with trimethylchlorosilane and sodium inrefiuxing toluene. In this process a Wurtz type reac tion results,whereby the trimethylsilyl group is attached to the phenyl ring with thesimultaneous production of sodium chloride.

The compounds of the formula RsSiOCI-IzCI-IR'OCoI-RCI 323 grams ofl-p-chlorophenoxy 2 propanol was dissolved in 200 ml. of dry toluene and99 grams of dry pyridine. 150 grams of trimethylchlorosilane was thenslowly added with shaking and cooling. Pyridine hydrochlorideprecipitated and was removed by filtration. The filtrate was mixed with150 grams of trimethylchlorosilane and the mixture was slowly added to62 grams of molten sodium in refluxing toluene. During the addition, themixture was vigorously stirred. Refluxing was continued for two hoursafter addition was complete. The mixture was filtered, and after removalof toluene and excess chlorosilane the compoundl-(p-trimethylsilylphenoxy) 2 propoxytrimethylsilane [p(CH3)3SiC'sH4OCI-I2CH(CH3)OSi(CH3)3] was obtained. This material had aboiling point of 176 C. at 24 mm., n L4'772, (14 .924, and a specificrefraction of .3057.

123 grams of the above ester was hydrolyzed in aqueous alcohol. Theproduct was taken up in n-hexane, dried, and cooled. Upon standing atroom temperature, crystals soon formed which had a melting point of 57C. to 59 C. Upon cooling the solution, more crystals having the samemelting point were obtained, giving a total of '72 grams. All of thecrystal fractions were combined and recrystallized to give a materialmelting 62 C. to 63 C. This material was l-(ptrimethylsilylphenoxy)-2-propanol [p- (CH3) 3SiC6H4OCH2CHOHCH3] Example 2 A mixture of 91grams of trimethylchlorosilane and 186 grams of2(p-chlorophenoxyethoxy)trimethylsilane was added slowly with vigorousstir- 'ring to 40 grams of sodium in 300 ml. of refluxing toluene. Afterthe addition was complete, refluxing was continued one hour, after whichthe mixture was filtered and distilled to yield 172 grams of2(p-trimethylsilylphenoxy)ethoxytrimethylsilane[p-(CHs)tSiCsI-IrOCHzCHzOSHCHah] boiling point 172 C. at 26 mm., 15111827, d4 .935, and a specific refraction of .3053.

172 grams of the above ester was hydrolyzed in an equal volume ofaqueous acetone containing hydrochloric acid. The hydrolysis mixture wassubsequently washed with water and distilled. There was obtainedhexamethyldisiloxane and 118 grams of p-trimethylsilylphenoxyethanol,boiling point 128 C. at .7 mm., n 1.5151, d4 1.001, and a specificrefraction of .3013.

Example 3 A mixture of 102 grams of trimethylchlorosilane and 209 gramsof o-chlorophenoxyethoxytrimethylsilane was added slowly with stirringto 42.5 grams of sodium in 300 ml. of refluxing toluene. The product wasworked up in the manner 3 m-ibed in Example 2 and there was obtained igrams of o-trimethylsilylphenoxyethoxytrithylsilane [0- (CH3)aSiCsH4OCH2CH2OSi (CH3) 3] ling point 166 C. at 24 m m., n L48l8, .9449,and a specific refraction 01 .3016.

103 grams of the above ester was hydrolyzed aqueous acetone with HClcatalyst. The hy- )IYSiS product was washed, dried, and distilled give55.5 grams of hexamethyldisiloxane and 3 grams of otrimethylsilylphenoxyethanol -CHa)3SiCsH4OCH2CH2OH], boiling point 106C. at .8 mm., n "1.5157, (14 111122, and a specific refraction of .2983.

That which is claimed is:

l. A compound of the formula where R is selected from the groupconsisting of methyl radicals and hydrogen.

2. p- (CH3) aSiCsH4OCHzCHOHCI-Ia. 3. p- (CH3) 3SiCsH4OCH2CH2OH. 4. 0-(CH3) 3SiCsI-I4OCH2CH2OH.

JOHN L. SPEIER, Jn.

No references cited.

1. A COMPOUND OF THE FORMULA